Metal working lubricants



H ass-m Forrest, Watson and Johnj E. wefi ei,,.;ise ikeiey, Francis C. Younger, El Cei'rito, Califl, assi noista' Shell Development Company, New York, N.Y., a corporation of Delaware No Drawing. Applie'ation-Tune 20, 1955 Serial No. 516,784

6 Claims. (Cl. 252-325) This invention relates to improved lubricating compositions and more particularly to lubricating oil compositions which are stable, non' c'orrosive non-staining and possess extreme pressure and anti-wear properties.

Lubricants which are commercially available for use where extreme pressures, high temperatures and high.

speeds are encountered, as in metal working operations or gear lubrication, are us'ually unstable, highly corrosive, cause staining and lack desired extreme pressure properties, thereby causing frequent tool or gear failure and contribute to other failures in the machine in which such lubricants are used.

It is an object of the present invention to provide an improved lubricating composition for use under extreme pressure and temperature conditions. Another object is to provide an improved lubricant, which is stable, iioricorrosive and non-staining towards metals. A still further object of this invention is to provide an improved metal working and gear lubricant which possesses good extreme pressure properties. Other objects of this invention will become apparent from the description of the invention.

Int accordance with the present invention, a superior extreme pressure' lubricant is obtained by incorporating into a mineral oil and/or sulfurized mineral oil, minor amounts of two primary additives, one being apar'tial ester of a polyhydric alcohol and a carboxylic acid and the other being a particular amine salt of a phosphorus acid represented by the general formula:

it I

in; A v wherein R is a hydrocarbyl or halohydrocarbyl and preferably a perhalohydrocarbyl radical, in which the carbon chain can range from -1- 'to 30 and preferably from 1 to carbon atoms; the Xs aretlie's'ame'or different divalent atoms of a non-metallic element of group VIB of the Periodic Table of Elements; of which-the elements oxygen and sulfur are preferred; and Y is hydrogen, R asdefined, o'r XH as defined. I w

The organic phosphonic and phosphinic acids having the above general formulaeanbe prepared by a -n' irnber of suitable. methods such as reportedby Arbuzov-t l. Gen. Ghent. (U'.S;S.R. 898-900, 1934 Coover; (Organic Qhmical Bulletin, Vol.23, No; 4;. 19551 Kosolapofis 60 Organic Phosphorus Qompounds (Wiley and Sons);

e'lssin g, to the corresponding nitmles rid fconve It has been found. that the "trtiar' ieeer'the invention. Aeeerqmg y,

\ 2,882,228 Patented Apr. 1 4,

ice

a s; Y rap er ait l nasty; s eaii bejpjrepar'ed b'y' oir "r "erred chain alcohols as p'redueed 'bjy' from bran hed en n cleans as fully des Slierwoo'dl'in the on a rduinal', 71, attain the February 19'531 nin as to the amine u catalytic hydrogenates method to convert 011613 to the Cbi'i' sft and "to form the amine-s derived? cunenai-ymahneis arena by essen amines, emailing, as his ternary air i i ca of'pol eemyl his, pal t.- are cularly effective for the pres nt' they constitute a preferred class of ii-itinli e ;,1',3 bu'tylarnin'e om the 8111123111011 bf 1.1 3 3 5 l v y 1,1,35,55,17:oetaaeta me n v tylen'ejand 1,1,3,3,5 ,5,7,7,9,9-deca p (from pentaisobutylene) are spectre pre'fe ed es, which arefsuit abl'y used individually [at as mixtures theta: of; In addition to these tert'i'" ii'msi'y primary tertiaryalliylme thylaimf" methyl pentylamine, 2,2,4,4,6',6-liex'a'met and the like are suitable. 5 w 1 Other tertiary br'a'nclie" chain allryl nn which can be used include the C and this type mentioned in Patents 2,160,058, 2,606,923 and 2,611,782, such as tertz tri'decylamine ennl-cnriF-d-Nm) as well as isoheptyldiethylearbinyl amine, isooctylethylpropylcarbinylamine, and the lilge. Primary amines of this type are commercially available from Rohm and Haas Company under the trade name of Primenes, specific products being Primene 8l-R, which is a mixture of primary alkylamines containing from about 12 to' 15 carbon atoms and Primene JM-R," which is a similar tertiary alkylamine mixture containing an average of about 18 to 24 carbon atoms.

The following are the properties of some amines which can be used to form the amine salts for use in lubricating compositions of this invention.

"!heseeondary amines whichcan be a ed form at, i

of'the phosphorus acids include ably aliphatic and cycloaliphatic amines, containing from lO to36 carbon atoms. diamy'lamine, dihexylamine, di(2-ethy lheryl) .amine, jdiqctylamine, didecylamine, didodecylami'ne, ditetradecyla ming? dihexadecylamine, dioctadecylarnine, dibromodi-" octadec'ylam'ine, isopropyloleylamine, diricinoleylamine, hi1tyli'icinoleylamine,' butyl-2-etliylhexylamine, .dila'urylamine, methyloleylamine, ethyloctylamine, isoamylhexyl amine, di'cycloliexylamine, dicyclorientylamine, cycloamine, beri'zy-PZ-ethylhxylamine, allyloctylarnine, do? dgcyl 2 ethylhexylamine, (1-isobtitylfB-methYlbtityI) 6,3, thyleyclojliei ylamine, di(l-isobu'tyl 3 f methylbutyh timing; N-n dodecyldiethylenetriamine, .N-nrtetradecyldi- Ifi-heaadecyl jtriethylene .te'trarnine, j heptyl t rirnethylene d n' ,N-'

rim yl ned a e'i-h nkniamhqflrida he. l e. j'f'Ihe phosphorus'acidsi used toformthe "partial or full amine salts include such compounds as haloalkanephoe phinic acids and haloalkanephosphonic acids such as trichloromethanephosphinic acid, ftrichloror'nethanthiophosphinic acid, 1,l-dibromoethanephosphinic acid, 3,3,5-' trichlorocyclohexanephosphinic acid, 1, 1-dichlorohexadccanephosphinic acid, 1,1-dichlorohexadecanephosphinic secon'd'ary'amines, prefer- Illustrative of such amines are.

thylenetria'mine,joctylethylne diamine, Ni- 2-ethylhexyl' ange l tripfropylene tetramine, mn'nt uyt acid, namely, one mole of the acid heating, Q S alts produced in the foregoing or equivalent manner can be purified by recrystallization from suitable solvents or other means which will be apparent to those skilled in the art. For exainple, trichloromethanephosphonic acid was reacted at a temperature of around 50 C. a mixture Of t-C1 H37NH2 t0 t-Cg4H4g'NHg in an amount suflicientto neutralize the total acidity of the amine. The product is represented by the formula OH-A":

or equivalently AH [GEO-got] This salt was completely soluble in mineral oil and p05 sessedfexcellent extreme pressureproperties. Using two 6 moles t-C12H35NH2 t0 t-C 5H NH in forming acid; trichloromethanephosphonic acid, 1,1-dichloroethanephosphonic acid, 2,2,Z-trichloroethanephosphonic acid, tribromomethanephosphonic acid, dichloromono bromomethanepho'sphonic acid, 1,1-dibromobutanephosphonic acid, 1,l-dichlorophenylethanephosphonic acid,

3;,13 5:trichlorocyclohexanephosphonic acid, 3, 5-dichloro cy lohexanephosphonie acid, l ,1 -dichloropropanephos phonic acid, 3,3,3-tribromopropanephosphonic acid, l,1- dichlordethanephosplionic acid, LI-dichlorobutanephosphonic a'cid, dichlorophenyl benzenephosphonic acid, 1,1-

as I

dichloroQ-monobromobutanephosphonic acid, Li dichlorooctanephosphonic acid, tricliloromethanethiophos phonic acid,1,l dibrornobutanethiophosphonic acid, 3,3,5- t'richlorocyclohexanethiophosphonic acid, 1,2-dichlor'oethanethiophosphonic acid, trichloromethaneselenophosphonic acid, and the like.

wherein R and X are the same as in Formula 1; R, can be hydrogen or, R as defined, and A is a long-chain highly branched aliphatic primary amine or aliphatic secondary amine, preferably having at least 8 carbon atoms and higher such as up to 30 carbon atoms in the molecule.

The amine saltsjof the acidic phosphono compounds and mixtures thereof as described can be prepared by interacting seIectedJamines with polyhalo-organo phosphoruscompounds as described above, as in a suitable solvent or in the presence of water and under suitable conditions such as mixing atroorn temperature, stirring or e phosphorus acid salts can be represented by the the above type of salt, the final product had the formula Ola-C- ORA:

or equivalently Another excellent extreme pressure additive having good oil solubility was prepared in the manner described above using only half the stoichiometric amount of amine (A required to neutralize the total acidity of trichlorornethanephosphonic acid. The product formed had the formula Y or equivalently A (Ch-C (OH) O) HQ The partial neutral primary highly-branched-chain amine salts which are specifically preferred include: 'ciz as z 12 25 2 is at n 18H37 2 to C H NH dimethyl neopentylcarbinyl amine, tert. tridecylamine salts of trichloromethanephosphonic acid, 1,1-dichloroethanephosphonic acid, 1,1-dibromobutanephosphonic acid, trichlorobenzenephosphonic acid, tribromomethanephosphonic acid, trifluoromethanephosphonic acid, tribromomethanephosphonic acid, trichloro methane-dithiophosphonic acid, chlorobenzene trichloromethanephosphinic, 1,1 dichloroethanethiophosphonic acid, trichlorobenzenephosphonic acid, trichloromethanephosphinic acid, dibromoethanephosphinic acid, and mixtures thereof.

The secondary amine salts which" are specifically preferred include: di-Z-ethylhexylamine, di-1-isobutyl-3- methylbutylamine, didecylamine, dioctadecylamine, isopropyloleylamine, butyl-Z-ethylheaylamine, dicyclohexylamine, l,l-dich1oroethanephosphonic acid, 1,1-dibromobutanephosphonic acid, trichlorobenzenephosphonic acid,

for tw'o moles of the massa e tribrbmom thanephosphonic acid, 'trifiubromethanephos phonic "acid, tribromomethanephosphonic acid, trichloromethane-dithiophosphonic acid, chlordbenzene trililoromethanephosphinic, 1,1 dichloroethanethiophosphonic *a'cid, trichlorobenzenephosphonic acid, trichloromethanephosphinic acid, dibromoethanep'h'osphinic acid, and mixtures thereof.

Although the primary and secondary amine salts are excellent for use in-compositions of this invention, when the secondary *amine salts are used, a solubilizer isgenerally'necessary. Sdlubilizers for this purpose, which do .not interfere with the extreme .pressure activity of the salts, are oil-soluble aliphatic alcohols and/or thiols, which can be saturated or unsaturated, straight or branchchain of at least '6 carbon atoms in the molecule. Branched-chain alkanols can be produced by the x0 process fully described by P. W. Sherwood in the Oil and Gas Journal, June 9,, 1949, page 71, and in the February 1953 issue of Petroleum Processing as well as in US. Patents 2,571,160 and 2,637,698. Other types of alcohols, such as the straight or branched-chain fatty alcohols, can be used "as well as their thiol analogues. Examples of suitable alcohols are: he'xyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, octadecyl,

ben'z'yl, 'cyclohexyl, dimethyl cyclohexyl, 3,3,5-trimethylcyclohexyl, oleyl alcohols, sperm oil alcohol, wool grease alcohol, 0x0 C -C alcohols (manufactured by Enjay Company and produced from olefins, carbon monoxide and hydrogen by "the 0x0 process), Archer-jDaniels-Midland *Adols which are higher fatty alcohols. The thiol analogues of these alcohols, such as described in US. Patent 2,638,448, and including iso-o'ctanethiol, decanethiol, octadecanethiol, tertiary tetradecanethiol, tertiary hexadecanethiol and the like or mixtures of said alcohols and/or thiols can be used with the phosphorus compounds in accordance with this invention.

The other primary additives, which produce a synergistic effect when used in combination with the phos- Ephorus compounds, are partial esters of polyhydric alcohols and organic carboxylic acids.

In general, there are utilized partial esters of fatty acids of from about 8 to 32 carbon atoms and wherein the ratio of esterified to 'unesterified alcoholic groups is :from about 1:5 to about 5:1, with those having a ratio of from about 1:2 to 2:1 being preferred, and particularly-partial esters of 0 43 fatty acids and aliphatic polyhydric alcohols.

One group of useful esters comprises those derived tram simple water-soluble alkanepolyols of from 2 to 6 "carbon atoms such as ethylene glycol, propylene glycol,

glycerol, erythritol, penta'erythritol, sorbitol, mannitol, dulcitol and the like. Another group of useful partial esters are those which are esters of water-soluble partially dehydrated '(etherified) polyhydric alcohols, including mixed ether-alcohols of different polyhydric alcohols.

Partial dehydration converts the simpler ones to linear ether-alcohols and some of the higher ones to an inner ether-alcohol. Thus, for example, ethylene glycol gives rise to diethylene glycol, triethylene glycol, etc., and mannitol, sorbitol and the like give rise to hexi'tans, such 'asi mannit'a'n and sorbitan. The hexitans can be etherified with alkylene oxides such as ethylene oxide or .glycol's to give mixed ether-alcohol. Still another group of partial esters suitable for the practice of the invention are the partial esters of water-soluble aldose and ketose carbohydrates generally referred to as the sugar esters.

The acids which can be used to make the partial esters from any of the above alcohols include aliphatic carboxylic "acids; cyclic organic carboxylic acids; aromatic carboxylic acids, sulf'onic "acids and the like. The aliphatic carboxylic acids include the monoand polycarboxylic acids of from 8 to 32, and preferablyfrom '10 to '20, carbon atoms and include saturated and unsaturated fatty acids of from about 10 to 20 carbon .phthalic, anthranilic acids,

atoms such as l au ric, steal-is, "olel'c and lindieie acids, s well as aliphatic polycarboxylic acids sueh "as a llke'nyl succinc acid, 'alkyl adipic acid and the like. The cyclic carboxylic acids 'tinclude naphthenic acids, such as cylohexane -.carboxylic acid, alkylcyclohexane carboxylic acids, Ialkylcyclopentane carboxylic acid, abietic acid and "the like. The aromatic acids include thesubstituted aromatic carboxylic acids such as benzoic, "salicyclic, the alkytated salicyelic and anthranilic acids in they kyl radicalis 'from 3 to 20 carbon atoms fbeiirg prefei'red o' I Specific esters derived from simple alkan" clude glycerol monooleate, glycerol zin'onost'earate, 'ilf glyc erol monoricinole'a'tje', .p'enta'erythritol monocaprylate, p'entaerythritol monoand dilaurat'e, per'itaerythritol monoand dioleate,:peiitaerythritol-"monm and 'd" t'eh'rate,

mono, di-, and triethyleneglycolmdnooleate, .p pylene mannitol monooleate, mannitol dioleate, sorbitol diol'eate,

etc.

Esters derived from ether-alcohols as "described may be prepared by .the method described "in US. T Patent 2,322,820. Examples of such esters which must contain at least one and preferably m'o'rethan one free 'hydroxyl group are sorbitan monoand dio'leate, sorbitan monoand dilaurate, mannitan monoand distearate, mannitan monoand dioleate, sorbitan monoand di'p'al'initate, sorbitan sesquioleate, sorbitan 'mononaphthenalte, mannitan monolaurate, etc.

Esters derived frornthe sugar snarl-'01s include glucose monooleate, glucose monoricino'leat'e, 'serbsse Tmonostearate, fructose monooleate and the like. I

If desired, minor amounts of secondary additives can be used in -coniunction with the two primary additives in compositions-of this invent-ion. Among such additives are the sulfurized and/or .su'lfoh'alogena't'ed fattylm'aterials such as animal, vegetable and marine fats and oils and derivatives thereof. Materials of this type canj be prepared by the methods described in US. Patents 2,322,859, 2,454,034, 2,459,717, 2,467,137,, 2,614,078, 2,644,825 and 2,7 01,237. Among such materials are sulfurized or sulfo-chlorinated fats fatty oils of the animal, vegetable and marine type and derivatives thereof, such as sulfurized or sulfo-chlorinate'd tallow, lard, lanolin, {jojoba oil, rapeseed oil, sperm oil, fatty acids of these fats and oils as well as their esters such as C 10 C saturated and unsaturated fatty acids, e.g., :my-rist-ic, 'sftearic, oleic acids, polymerized fatty acids suchas polymerized linoleic acid or Empol 1022 which-is a polymerized fatty acid made by Emery Industries; or esterssuch as cetyl stearate,

cetyl oleate and mixtures thereof; halogenated sis, bits,-

waxes such as chlorinated p'araffin wax, 'tihlofl ated tal-' low, etc., of these "materials preferred are the fsulfurized sperm oil, lanolin, rapeseed oils, oleic acid chlorinated paraffin wax and cetyl oleate as well as mixtures thereof.

In addition, various oil-soluble anti-oxidants, e.g., alkyl phenols; corrosion inhibitors, e.g., mercaptoben'zothiazole and salts thereof, diisoprofpyl ammonium'nitrite, (l -C fatty acids; anti-foaming agents, e.g., silicone polymers, organic phosphates, aliphatic alcohols and the like, can be used.

Base oils to which agents of this invention are added may be selected from a variety of natural oils such as paraflinic, naphthenic and mixed base mineral oils having a viscosity range such as from 5:0 SUS at R, up to 250 SUS at 210 F. .In addition, synthetic oils may be used such as polymerized olefins, alkylated aromatics; polyalkyl silicone polymers, e.g., liquid dimethyl silicone ether; esters, e.g., di(2-'e'thylhexyl) sebadare. Mixtures er natural and "synthetic oils can the of this invention:-

Amounts, Percent Wt.

Components General Preferred Yrimaryddditlvesr Amine salt o1 phosphonlc or phosphlnlo 1" M 0.1- 1-5 1 'Partlal..tester.ot polyhydrtc alcohol and; 1

organic carboxylt acid or organic suljurlzed acid... 0. 1-10 1-5 SeoondaryAdditives Alcohol solublllzers. 0-5 1-4 Sulfurized tattymaterialuhsr 0-10 1-5 -A.ntl-oxldnnt, corrosion inhibitor, antl- :-.B .,stalnlng agent... 0-1 0.1- Lubricating oil and/or sulfur-iced lubricatlnz.oll..-.-. Balance Balance Specifi "Composition A: 0.5% sulfurized oleic acid f 1.0% glycerol monooleate ,.I 0.75 trichloromethanephosphonicacid 1.40% Alkylamine 81 (see Tablel) Bal. SAE '90 mineral oil Composition B:

I 0.5% sulfurized oleic acid 1.0%. sorbitan dioleate i 0.75% trichloromethanephosphonic acid -l.40% Alkylamine 81 (see Table I) Composition C:

0.5% polymerized fatty acid 0.5% glycerol monooleate 0.75% trichloromethanephosphonic acid 1.40% Alkylamine 81 (see Table I) p 1.75% chlorinated paraflin wax Bal. SAE 90 mineral oil 1 Composition D:

0.5% polymerized fatty acid (Empol 0.5% sorbitan dioleate 0.75 trichloromethanephosphonic acid 1.40% Alkylamine 81 (see Table I)* 1.75% chlorinated'paraflin wax f'-- Bal. SAE 90 mineral oil- Composition E:

' 1 0.2% glycerol monooleate 0.75 %-trichloromethanephosphonic acid 2.6% Alkylamine JM (see Table I) .1 1.75% chlorinated, paraflin wax Bal. SAE 90 mineral oil Composition F: l

1.0% glycerol monooleate 0.75 trichloromethanephosphonic acid 1.40% Alkylamine 81 (see Table I) Bal. SAE 70 mineral oil Composition G:

1.0% sulfurized sperm oil 1.0% glycerol monooleate "0.75% trichloromethanephosphonic acid 0.70% Alkylamine 81 (see Table I) i 0.2% 2-mercaptobenzothiazole Bal. sulfurized pale oil (80 SUS at 210 F.)

' Composition H:

' 1.0% glycerol monooleate 0.75% trichloromethanephosphonic acid 0.70% Alkylamine 81 (see Table I) 0.2% 2-mercaptobcnzothiazole Bal. sulfurized pale oil (80 SUS at 210 F.)

The superiority of compositions of this invention as extreme pressure and corrosion resistant lubricants is evidenced fromthe data presented in Table H. Theex'treme pressure properties of the compositions tested in Table H were determined in the'four-b'all extreme pressure tester c examples-of compositions of this invention are:

monostearate.

described in --Engineering, vol. 136, July 13, 1933, and in corrosion resistant properties of the compositions were determined by the L-l3 test described in the CRC Handbook.

; Table II Four-BallTest: .L-13'. IflHypoldGear Tostll Compositions Initial Seizure Corrosion (H.P.). .r, 'Load(Kg.) Test 141-158 Passed.-- 140+ 140+. gelled immediately.

. 28. i Failed immediately.

om te 4=Mineral oll (SAE Compositions G and H were used in a thread cutting machine and excellent threading of mild steel at speeds of over-1,025 r.p.m. was achieved, while with compositions'l to 4 threading was poor at speeds of less than 400 r.p.m. I Similar results to those for compositions A to H'in the above tests can be achieved by substitution for the trichloromethanephosphonic acid of other acids such-as trichlorobenzenephosphonic acid, butyl trichloromethanephosphonic acid, trichloromethanephosphinic acid; and for the Alkylamine 81 or J M of such amines as tertiaryoctylarnine, di-Z-ethylhexylamine, dicyclohexylamine; and for the glycerol monooleate or sorbitan dioleate such esters as pentaerythritol monooleate, sorbitol monooleate, mannitan monolaurate, glucose monooleate and Zsorbose Under certain conditions of lubrication, the addition of polyhydric alcohols, such as alkyl glycols, erythritol, glycerin, hexitols and the like, is most advantageous. This is particularly applicable where the lubricating .compositions are used under extremely high temperatures and heavy load conditions. a

Theadditive combination of this invention also can be used to improve turbine oils, process oils, industrial oils, hydraulic fluids and heat transfer fluids.

We claim as our invention: h

1. A lubricating oil composition comprising a major amount of a mineral lubricating oil containing from about 0.1% to about 10% each of a long chain highly branched primary tertiary aliphatic amine of at least8 carbon atoms salt of a chloromethanephosphonic acid, and a partial ester of a polyhydric alcohol having froin 2 to 6 carbon atoms and a C -C fatty acid.

2. A lubricating oil composition comprising a major amount of a mineral lubricating oil containing from about 0.1% to about 10% each of a long chain highly branched primary tertiary aliphatic amine of at least 8 carbon atoms salt of trichloromethanephosphonic acid and a partial ester of a polyhydric alcohol having from 2 to 6 carbon atoms and a C -C fatty acid. I I

3. A lubricating oil composition comprising a major amount of a mineral lubricating oil containing from about 0.1% to about 10% each of a long chain highly branched primary tertiary aliphatic amine of atleast 8 carbon atoms salt of trichloromethanephosphonic acid and glycerol monooleate.

4. A lubricating oil composition comprising a major amount of a mineral lubricating oil containing'from 9 branched primary tertiary aliphatic amine of at least 8 carbon atoms salt of trichloromethanephosphonic acid and sorbitan dioleate.

5. A lubricating oil composition comprising a major amount of a mineral lubricating oil containing from about 0.1% to about each Of t'C 2H25NH to t-C15H 1NH salt of trichloromethanephosphonic acid, glycerol monooleate and sulfurized sperm oil.

6. A lubricating oil composition comprising a major amount of a mineral oil containing from about 0.1% to about 10% each of a long chain highly branched tertiary aliphatic amine of at least 8 carbon atoms salt of a 10 chloromethanephosphonic acid, a partial ester of a polyhydric alcohol having from 2 to 6 carbon atoms and a C -C fatty acid and sulfurized sperm oil.

References Cited in the file of this patent UNITED STATES PATENTS 1,463,092 Pelly July 24, 1923 2,249,800 Weber July 22, 1941 2,479,424 Sproule Aug. 16, 1949 2,515,115 Davis July 11, 1950 2,683,691 Thorpe July 13, 1954 

1. A LUBRICATING OIL COMPOSITION COMPRISING A MAJOR AMOUNT OF A MINERAL LUBRICATING OIL CONTAINING FROM ABOUT 0.1% TO ABOUT 10% EACH OF A LONG CHAIN HIGHLY BRANCHED PRIMARY TERTIARY ALIPHATIC AMINE OF AT LEAST 8 CARBON ATOMS SALT OF A CHLOROMETHANPHOSPHONIC ACID, AND A PARTIAL ESTER OF A POLYHYDRIC ALCOHOL HAVING FROM 2 TO 6 CARBON ATOMS AND A C10-C20 FATTY ACID. 